Polyamide-like condensation products and process for preparing the same



Patented June 7, 1960 In other words, a dicarboxylic acid can be formed that 2939 853 also contains an ester radical and a secondary alcohol Q radical. When using epoxy fatty acids, an intermolecular POLYAMIDE-LIKE CONDENSA PRODUCTS reaction between epoxy radicals and carboxyl radicals AND PROCESS FOR PREPARING THE SAME 5 of the epoxy fatty acid may occur. In this reaction Hermann Delius, Hamburg, Germany, assignor to Reichlactide-like compounds are formed. The formation of bold Chemicals, Detroit, Michcyclic lactones as the result of an intramolecular reaction No Drawing. Filed Ap 17, 1956,s -,N 578,560 seems less likely. With due consideration to this side Claims riori a HcafionG rm F b. 18 1956 reaction, wh1ch obviously has an ummportant influence p Z e any e on the end result, the use of epoxy fatty acid esters Claims 260-18) doubtless possesses the advantage that no lactides or possibly lactones can be formed.

The invention relates to the process of preparing cer- In Working With a 2:1 molar ratio of epoxy fatty acid tain novel polyamide-like condensation products and is to dicarboxylic acid, a reaction approximately according in the nature of an improvement on the disclosure of to the following diagram is to be predominantly expected:

=0 ole).

OH b

. omoHm-bHJmomrco0H the application of Wolfgang Foerster Serial No. 567,750, What has been said above concerning the 1:1 reaction filed February 27', 1956. ratio is also valid here, as regards the intramolecular In said application Serial No. 567,750, filed February 30 reaction, for possible participation of the carboxyl radi- 27, 1956, a process for the preparation of novel, polycals of the epoxy fatty acids in the reaction with the amide-like condensation products is described. The parepoxy radicals. Likewise, in the abovesense, the use ticular characteristic of this process consists in condensof epoxy fatty acid esters here also favors a connection ing unsaturated epoxy fatty acids or their esters particuof two fatty acid residues over a dicarboxylic acid ester larly the esters of monoalcohols having a boiling point radical.

not exceeding 200 C. with di, tri-, or higher polyamines. The reaction temperature for this first stage of the In developing the basic idea of the invention, it has present invention lies between 100-200 0, preferably now been found that it is advantageous first to react the at 150 to about 200 C. The drop in the acid number unsaturated epoxy fatty acids or their monoalcohol esters 40 is a convenient measure of the progress of the reaction. with dicarboxylic acid and to subject the reaction prod- Especially when epoxy fatty acids are used, the reaction ucts obtained in this manner to amidation with di-, tri-, should be interrupted upon reaching'a certain level in the or higher polyamines. V acid number, whose value lies about 20-30 units above It is known that carboxyl radicals react with epoxy the theoretically calculated one. Otherwise an additional radicals. With a monocarboxylic acid this reaction proesterification of free carboxyl radicals with thesecondary ceeds approximatelyasfollows: hydroxyl radicals that result from the reaction of the i epoxy radicals will take place, which can lead to gelatini- 3H (SHOOC-R zation of the ingredients by polymerization. In the reaction of epoxy fatty acid esters with dicarboxylic acids,

H HOE it is uneconomlcal and inadvisable to permit the reaction tlohi reach the theoretical aC1d1111lII1b6 l 0 1; the first silage.

. Y s reaction is appropriate y terminate upon reac ing $5 2: s g gi g 2 3: 0 3 g g ig g g g i; 2 :5 2? an acid number of about 20. The reaction products obtained in the first stage are subsequently reacted at higher an e ox fatt acid monoalcohol ester. Basicall all the g i digarboxylic acids are Suitable; however}: the temperatures with ethylene dlamlne, diethylene triamine reaction proceeds most advantageously with dibasic acids gf F g fla Y i every case that easily give a homogenous mixture with the epoxy so u e an 51 e resm' 1 p0 yamlde-h e condensafatty acids or their esters under the temperature and products that elther alone or m mlxture i reaction conditions described below. As examples the raw mammals represent valuable novel Synthetlc following may be mentioned: succinic acid, glutaric acid, 1.651115 E l 1 adipic acid, azelaic acid, sebacic acid, isosebacic acid xamp e (a mixture of branched isomeric C -dicarboxylic acids), 300 g. epoxy soy bean fatty acid (oxirane-oxygen conphthalic acid, etc. tent 3.94%, acid number 143) and 107.5 g. adipic acid If epoxy fatty acids or their monoalcohol esters are are gradually heated to 200 C. with stirring, an inert gas, reacted with dicarboxylic acid in a 1:1 molar ratio, about such as nitrogen or carbon dioxide, being forced through the following schematically illustrated reaction takes and kept at 200 C. until the acid number of the reaction place predominantly: product has dropped to 205-215. Thereupon the reaction product is allowed to cool to about 80 C., and 154.5 g. diethylene triamine are added. Now the reaction mixture is heated under reflux to a temperature of 140 C. After a lapse of 2 hours the temperature is raised to 200 C. in the downtake cooler and kept there for about 2 hours. In order to remove small amounts of low-molecular constituents possibly causing trouble later on, these are distilled ofi during the second hour by working under a vacuum. After cooling, a light yellow, soft resin is obtained. The yield amounts to about 480 g. The conden'sation product dissolves well in mixtures of aromatic substances and aliphatic alcohols, e.g. in a 1:1 mixture of 'toluol and i-but'anol.

Example 2 620 g. of epoxy soy bean fatty acid methyl ester (oxirane-oxygen content 6.5%) and 504 g. sebacic acid are heated together as described in Example 1 until an acid number of 125-130 has been reached. After cooling to 70-80 C., 257 g. diethylene tn'amine are added and, as described in Example 1, heated. Av light-colored soft resin results. Approximate yield: 1100 g.

Example 3 620 g. epoxy linoleic fatty acid methyl ester (oxiraneoxygen content 6.1%) and 172 g. adipic acid are heated to 180 C. and kept at this temperature until the acid number has dropped to a value 20. After cooling to 70-80 C., 206 g. diethylene triamine are added and the process, continued as described in Example 1. Yield: approx. 850 g. of a light-colored soft resin.

Example 4 600 g. epoxy soy bean fatty acid (oxirane-oxygen content 4.2%, acid number 119) and 115 g. adipic acid are heated to 180 C. with stirring under a stream of inert gas and held .at this temperature until an acid number of -130 has been reached (theoretical value: 100). Then heating is discontinued and the temperature allowed to drop to 80 C. At this temperature, 206 g. diethylene triamine are allowed 'to flow in, and the process is continued as described in Example 1. Yield: about 800 g. of a light-yellow colored resin that possesses about the same consistency as the condensation products described in the other examples.

The invention has been described in detail for the purpose of illustration but it will be obvious that numerous modifications and variations may be resorted to within the scope of the appended claims.

I claim:

1. A process for the preparation of polyamidedike condensation products which comprises reacting (1) at least one member of a group consisting of epoxidized fat acids and esters of epoxidized fat acids of saturated 4 monohydric aliphatic alcohols having a boiling point not above about 200 C. and (2) at least one member of a group consisting of hydrocarbon dicarboxylic acids having not more than 10 carbon atoms in a mol ratio of 0.5 to 1.0 mol of dicarboxylic acid per mol of oxirane groups in said epoxidized fat acids and esters under elevated temperature conditions of about 200 C. until an acid number of not more than 30. is obtained above that theoretically obtainable, cooling the reaction product to between about and about f C, adding a polyamine having the formula l ?-NH-CH CH -NH wherein R is fa member of the group consisting of H and --(CH '+CH --NH heating the resultant mixture at temperature of about 200 C. and terminating the reaction while the said condensation product is still fusible.

2. A polyamide-like condensation product produced in accordance with the process of claim 1.

3. A process for the preparation of polya'm'ide-like condensation products which comprises reacting (1) at least one member of a group consisting of epoxidized fat acids and esters of epoxidized fat acids of saturated monohydric aliphatic alcohols having a boiling point not above about 200 C. and (2) at least one member of a group consisting of aliphatic dicarboxylic acids having not more than 10 carbon atoms in 2 mol ratio of 0.5 to 1.0 mol of dicarboxylic acid per mol of oxirane groups in said epoxidized fat acids and esters under elevated temperature conditions of about 200 C. until an acid number of not more than 30 is obtained above that theoretically obtainable, cooling the reaction product to between about 70 and about 80 C., adding a polyamine having the formula R-'NHCH -CH -.-NH

wherein R is a member of the group consisting of H and -(CH -CH -NH heating the resultant mixture at a temperature of about 200 C. and terminating the reaction While the said condensation product is still fusible.

References Cited in the file of this patent UNITED STATES PATENTS ress in the Chemistry of Fats and Other Lipids, pages 213-217, Pergamon Press Ltd., London (1955).

Chemical Abstracts, volume 39, No. 24, pages 5923 5924 (1945), Lee et al., Epoxy Resins, page 31, McGraw- Hill (1957). (Copy in Science Library.) 

1. A PROCESS FOR THE PREPARATION OF POLYAMIDE-LIKE CONDENSATION PRODUCTS WHICH COMPRISES REACTING (1) AT LEAST ONE MEMBER OF A GROUP CONSISTING OF EPOXIDIZED FAT ACIDS AND ESTERS OF EPOXIDIZED FAT ACIDS OF SATURATED MONOHYDRIC ALIPHATIC ALCOHOLS HAVING A BOILING POINT NOT ABOVE ABOUT 200*C. AND (2) AT LEAST ONE MEMBER OF A GROUP CONSISTING OF HYDROCARBON DICARBOXYLIC ACIDS HAVING NOT MORE THAN 10 CARBON ATOMS IN A MOL RATIO OF 0.5 TO 1.0 MOL OF DICARBOXYLIC ACID PER MOL OF OXIRANE GROUPS IN SAID EXPXIDIZED FA ACIDS AND ESTERS UNDER ELEVATED TEMPERATURE CONDITIONS OF ABOUT 200*C. UNTIL AN ACID NUMBER OF NOT MORE THAN 30 IS OBTAINED ABOVE THAT THERETICALLY OBTAINABLE, COOLING THE REACTION PRODUCT TO BETWEEN ABOUT 70* AND ABOUT 80*C., ADDING A POLYAMINE HAVING THE FORMULA R-NH-CH2-CH2-NH2 WHEREIN R IS A MEMBER OF THE GROUP CONSISTING OF H AND -(CH2-CH2-NH2), HEATING THE RESULTANT MIXTURE AT TEMPERATURE OF ABOUT 200*C. AND TERMINATING THE REACTION WHILE THE SAID CONDENSATION PRODUCT IS STILL FUSIBLE. 